Manitfacttjke of cyanogen compounds and ammonia



2 Sheets-Sheet 1.

Patented A1390.19

L. MOND.

MANUFAOTURE 0F OYANOGEN COMPOUNDS AND AMMONIA.

(No Model.)

2 sheets-sheet '2. L. MOND.

MANUFACTURBOF GYANOGEN' COMPOUNDS AND 'AMMONIA No. 269,309. PatentedDec.19,'188`2.

.w 11mg HUM..

(No Model.)

UNITED STATES PATENT OFFICE..

LUDWIG MOND, OF VINNINGTON HALL, NORTHWICH, COUNTY OF CHESTER,

ENGLAND.

MANUFACTURE OF CYANOGEN COMPOUNDS AND AMMONIA.

SPECIFICATION forming part of Letters Patent No. 269,309,5dated December19, 18.82,

Application filed January 28, 1882. (No model.) Patented in BelgiumJanuaryv 28, 1882, No. 56,919; in England January 2B, 1889, No. 433; inFrance January Q8, 1882, No. 141,105; iu Austria-Hungary May 25, 1882,No. 20,196 and No. 4,708.

To all whom it may concern: diameter;v orI mix the'carbon and bariumcar- Beit known that I, LUDWIG MOND, of VVinbonate on the bed of afurnace in a reducingnington HalhNorthwich, in the county ofOhesdametill the carbonate melts and formsapasty ter, England, manufacturingchemist, have inor viscous mass with the carbon, when itis with- 55 5vented a new and useful Improvement in the drawn, cooled, and broken up.

ManufactureofCyanogen Compounds andAm- The change to cyanogen compoundcan be 1nonia,ofwhich the following is a specitication. accomplished invarious ways. One plan is to 'Ihisihvention consists in improvements onpile the materials in chambers. kilns, or ovens the process of obtainingbarium cyanide and of convenient` shape, preferably kilns of the 6o ioantimonia patented by Messrs. lllargueritte type known as a continuouskiln,77 consisting` and Saurdeval in Great Britain, No. 1,027 of ofnumerous chambers, some of which are be- 1800, which consistsin heatingbarium carboning heated while the others are being cooled, ate or bariumoxide, intimately mixed with filled, or emptied. A chamber being tlled,it carbon in an atmosphere of nitrogen to an eleis heated by passingthrough it a gas which 65 r3 rated temperature, whereby a compound orhas been elevated toa high 'temperature-say compoundsotbarium andcyanogen are formed, 1,400O centigrade-bet'ore entering` the chamandthen treating the material by steam at a ber, said gas containing as'much nitrogen as temperature ot' trom 3000 to 5000 centigrade, possiblewith the smallest practicable amount whereby ammonia is liberated. AThisprocess of oxygen, carbonio acid, or vapor of water. 7o 2o failed tosucceed commercially, owing, among Fuel can be economized both inheating and in otherreasons, tothe materials being used in the coolingon thc well-known principle used in conpulverulentform,and being thusapt tocake or tinuons kilns. Vhen a suiiicient amountof cychoke or causethe gas to act imperfectly,aud auogen compound has been formed the hotgas also owing to the various operations being peris sluit ott', andcool gas of the same or similar. 75 25 formed in one retort, which wasconsequently composition is passi d through until the temsubjected tofrequentandgreat changeset' tem- .perature is reduced to below 5000eeutigrade', perature, causing great waste of fuel and wear when thesupply of gas can be shut ofl and the and tear. To ebviate these defectsI tiist make materials treated with steam to liberate ammomy materialsinto bricks or lumps, and when nia, which is drawn out by means of anaspira- 8o 3o using retorts form the cyanogen compound in tor andcondensed or absorbed as desired; or one retort or upper part of theretort only and the current of cold gas is continued until the cool itin a second retort or chamber connected material is sufficiently cool totake it out ofthe with the nrst, or in the lower part ot' the retort,chamber, (in any case below 3000 centigrade.)andeitherformtheammoniainthebottomot'the It is then heated with steam ina suitable ap- 85 .35 cooling-space or in aseparate apparatusaltoparatus-say an iron retort-at a temperature gether. In making thebricks or lumps I take ot' from 3000 to 500O centigrade. The ammonia thebarium carbonate and carbon, preferably given otf in this operation canbe collected in finely pulverized, and, if desired by the opersulphuricacid orin anyother well-known manator, mixed with a quantity ofcarbonate of ner. After this treatment thc bricks can be. 9o 4ostrontia, magnesia, orlime, but preferably magrepeatedly subjected tothe same treatment unnesia-,soas tomakethem lessfuslble asa'whole, tilthe carbon is sufficiently exhausted, when and when mixed form them intoblocks with they are ground up with fresh carbon and pitch as anagglutinating substance, molding pitch and made into bricks again; orthe)` may them hot,asisdonewithpatentfuelfand prefbe remadeattereaohoperation by replacing the 95 45 erably heat these blocks in areducing-flame carbonaceous materials consumed.

toa degree sufcient to coke the pitch, or, still As a source ot'nitrogen I prefer the gases further, until a part or all of the bariumcarescaping from the manufacture of sodium bi` bonate is converted intobarium oxide. It' carbonate by the ammonia process.' 'Ih'esenecessary,when cold, break these blocks up to gases may be heated to therequired temperaroo 5o the requisite size-say lumps of such size as tureby any known means, preferably a Sie` willpass through aring about threeinchesin mens regenerator; or I` use the products of combustion of coalor coke with a minimun quantity of air, so that they contain as littlecarbonio acid and vapor of water as possible. These gases may beobtained at the required temperature bypassing them through aregenerator or other heating apparatus, or preferably by previousheating of the air used in the combustion of the fuel. In this latterease these gases, after leaving the last kiln used at the time forheating the material, are cooled by passing them under boilers, pans,&c., or through a scrubber down which water is running, before they areintroduced into the kiln or kilns in which at the time the material iscooling.l Having served for this latter purpose, the gases, whichconsist largely of carbonio acid, can be used as a source of heat-sayfor heating the air, raising the steam, and heating 'theammonia-genera-ting apparatus in the process under eonsideration-or forany other purpose.

In some cases it may be found convenient to use the hot gases obtainedfrom gas-producers, as described, for heating the material used toet'tect the cooling, or bythe gases obtained from the manutactureotbicarbonate ot'soda by the ammonia process, or by any other gases of therequired composition which may be availv able. A modir'ation of thisplan(uset'nl especially in small works) consists in forming the bariumcyanide in a retort or-chamber the,y

upper part ot which is heated externally, while the lower part is notexposed to the heat, but, on the contrary,iscooled preferably bothexternally and internally, as will be hereinafter described. The.material is cooled in its passa-ge through the. lower part, and near thebottom is exposed to the action ot' steam; or the material is carried,when sufciently cooled, to an independent apparatus to be steamed.

In place ot' steam. a spray ot' Water, or mixture ot' steam and water orof nitrogen and water, may be introduced.

'lhis system and apparatus can be best described by aid oftheaccompanying drawings, in which Figure l shows a sectional plan throughW X ot' Fig. 2, and Fig. 2 a vertical section through Z'Y ot' the. plan.

A A are clay retorts set in four rows in heating-chamber B. c c are theentrance-holes for the gas and air, preferably brought from a Siemensregenerator; D D, diaphragms or partitions ot' tire-clay placed betweeneach pair ot rows ot' retorts to force the products ot' combustion toascend round one row and descend round the otherA to the exit-holes E;E, exitholes carrying' the products ofcombustion back to regenerator. HH are the lower portion of the retort A, preferably made of iron, whichcan he surrounded by water or cooled by a blast ot' air or spray fromroses 'I T, placed in any convenient position as found most convenient.I is the pipe 'tl1rough which cold gases rich in nitrogen are passedinto the cooling part ofthe retort or chamber; J, a stop-cock, and Kentrance for steam. These are not necessary parts of the apparatus, andare only used when the steaming is performed in the lower part ofthechamber instead of in a separate apparatus, such as I prefer to use.

K represents the entrance for steam when used; L, junction or entrancefor gases, some times used in an alternative mode of working, asexplained farther on; M, escape for ammonia. P Q are the Iines supplyinggas and air, respectively, from the regenerator; R, the exittubescarrying the waste gases back to the regenerator; S, doors of retorts.

The mode of action is as follows: The retorts or chambers A and H beingnearly filled with blocks which have already undergone thecyanide-forming process, the upper ends of retorts A are filled withfresh hriquettes or lumps ot' barium carbonate or oxide and carbon. Theheat in the heating-chamber B is maintained to from 1,1000 to 1,4000centigrade, and gases rich in nitrogen are passed through entrances I Iinto the chambers Il H. As the briquettes get hot the nitrogen reactsupon them, and a compound of barium and cyanogen is formed.

-From time to time material is abstracted from the bottom ot' chamber Hand fresh material inserted at the top of A. Usually the materialabstracted (which should have been reduced below 3000 eentigrade, as ata higher temperature it would be almost instantly decomposed by contactwith air) is taken to other apparatus, heated in aretort to 4000 or h@eentigrade, and then treated with common or superheatcd steam or. withsteam and spray, as may be found best in practice in each works, thetemperature ot' the cyanide being raised and maintained higher whensteam and spray are used than when superheated steam is employed. It',however, (though I do not prefer it,) it is desired to do the steamingin the lower part of the ehamber H, I so arrange the temperature ofthenitrogen and the. external cooling agents that the materials in thechamber H, when they descend ['i-astthestopcock J, shall be at atemperature ot' about 400O to 5000 centigrade. I then pass in steamthrough orifice K. This steam must'be of less pressure than the nitrogenentering at I, or the stop-cock J must be closed when the steamis on, asit is very undesirable that the steam should rise up among the hotmaterial. The steam is passed downward through the materials, and theammonia formed leaves by orifice M. Then the steam is sluit off, thestop-cock is closed, and that portion ofthe materials hitherto exposedto the action ofthe steam is withdrawn. The stop-cock is then opened andthe material allowed to descend to till the void, afresh charge isinserted at the top' of A, and the operation goes on as before. l

In some casts-instead of cold nitrogen being introduced at I, it may befound desirable to introduce a het mixture of nitrogen and carboniooxide as free as possible from oxygen, vapor of water, or carbonic acidthrough pipe L.

NVith regard to the foregoing, I would remark that when cold nitrogen isintroduced at IOO Irs

I it rises up among the hot material, cooling the latter and beingheated in its turn till, as it enters A, it is very hot, thuseconomizing fuel on the principle ot' the continuous kiln recommendedfor working on a large scale. In the alternative plan of introducing ahot mixture of nitrogen with carbonio oxide at L less heat need betransmitted through the walls of the retorts, and the yield of theappararus will be much increased. This will, however, necessitate morecooling space or appliances. The gases given oi at the top of A and Nare also richer in carbonic oxide when the hot gases, as abovedescribed, are introduced into the retort, and they can be moreprottably used for heating purposes.

- It is important that the carbonaceous matter should be as free aspossible from silica. I prefer therefore to use coke obtained from pitchor oil. It is also advantageous to mix some sawdust with the materialsforming the brick to make the latter more porous.

The most favorable proportions for the materials forming the bricks areone hundred and sixty-three of barium carbonate, forty-three carbon, andfifty-eight pitch. The addition ot' carbonate ofstrontium, calcium, ormagnesium is not necessary; but some can be added in quantities to suitthe operator. Less care need then be exercised to prevent the fusing ofthe barium carbonate by too great heat.

Throughout this specitication I have only spoken of barium. Theinvention is, however, also applicable with little modification ifpotassium or sodium be used instead of barium, and possibly at extremelyhigh temperatures some ofthe other alkaline earths might be substitutedfor barium. ln practice, however, I have found barium so much superiorto even the metals of the alkalies that I did not consider it worthwhile doing more than merely mentioning the alkaline metals as in thiscase a barely practicable and "ery poor chemical substitute for barium,and one which I would not advise the adoption of except underextraordinary circumstances.

I am aware that partitions have been employed between vertical retortsin gas-retort ovens to cause the products of combustion from the furnaceto travel up to the top and down to the bottom of the oven in acircuitous path,.and this I do not claim; but I believe my particulararrangement of the air and gas lines, together with the oven anddiaphragm, constitutes a structure new as a whole.

Having thus described my invention, what I do claim isl. In the processof manufacture of eyanogen compounds or ot' ammonia therefrom,form inginto blocks an intimate mixture of carbon, carbonate or oxide of barium,and of a refractory basic absorbing material-such as magnesia-andpreliminarily calcining the same out of contact of air before exposingthem in the heated state to nitrogen for the formation of the cyanogencompounds.

2. In the manufacture of cyanogen com? pounds of barium or of ammoniatherefrom, the preliminary heating of the mixture of barium carbonate oroxide and carbon in a re- 7o ducing-tlame until they form a pasty mass,and the breaking up of the mass after cooling into lumps for theformation of cyanogen compounds by contact with nitrogen at an elevatedtemperature. 7 5

3. The combination ot' the gas and air tlues I and Q, the retorts A, thediaphragm D, and the exit-holes E at the bottom of the chamber, by whichmeans the gases have to circulate up among one range of retorts and downamong 8o the next set before escaping.

4. The combination, with the iron coolingchamber H, connected with theclay retort A, of a device, T, for sprinkling the said chainber H withune spray, for the purposes detween. 9o

6. The combination ofthe pipe I, supplying nitrogen at a pressure abovethe atmosphere,

.stop-cock J, not entirely closing the passage,

chamber H, and door S, for the purposes described'. 9 7. The improvementin the manufacture ot' cyanogen compounds by means ot' barium salts oroxide and carbon, which consists in first heating the nitrogenous gasesbefore entering the converting-chamber by passing them Ico through thehot barium salts, said salts being thereby cooled, and immediatelypassing these gases through fresh layers of barium salts and carbon atthe temperature required to form cyanogen compounds.

S. In apparatus for manufacturing ammonia, the combination ot' acyanogen-formin'g` retort or chamber, A, a cooling-chamber, H, belowthat, and an ammonia-fbrming chamber below the cooling-cham ber,separated from the 1 1o cooling-chamber b v a valve or cock and from theouter air by a lid.

9. The improvement in the manufacture of ammonia by means of bariumsalts and car-- bon, which consists in using the same nitrog- I 15 enousgases successively for forming the cyanogen compounds, for heating thebarium salts and carbon to the desired temperature, and for cooling thecyanogen compounds after they are formed.

10. The improvement in the manufacture of cya-nogen compounds by meansot' barium salts or oxide and carbon, which consists in cooling the hotcyanogen compounds by passing through them nitrogenous gases as free aspos- 1275 sible from oxygen, carbon dioxide, and vapor of water, wherebythese gases become heated.

LUDWIG MOND.

Witnesses:

WM. P. THOMPSON, W M. MAKEPEAGF. EDWARDS.

